Guangliang Liu

Complexation of arsenite with dissolved organic matter: conditional distribution coefficients and apparent stability constants.

The complexation of arsenic (As) with dissolved organic matter (DOM), although playing an important role in regulating As mobility and transformation, is poorly characterized, as evidenced by scarce reporting of fundamental parameters of As-DOM complexes. The complexation of arsenite (AsIII) with Aldrich humic acid (HA) at different pHs was characterized using a recently developed analytical technique to measure both free and DOM-bound As. Conditional distribution coefficient (KD), describing capacity of DOM in binding AsIII from the mass perspective, and apparent stability constant (Ks), describing stability of resulting AsIII-DOM complexes, were calculated to characterize AsIII-DOM complexation. LogKD of AsIII ranged from 3.7 to 2.2 (decreasing with increase of As/DOM ratio) at pH 5.2, from 3.6 to 2.6 at pH 7, and from 4.3 to 3.2 at pH=9.3, respectively. Two-site ligand binding models can capture the heterogeneity of binding sites and be used to calculate Ks by classifying the binding sites into strong (S1) and weak (S2) groups. LogKs for S1 sites are 7.0, 6.5, and 5.9 for pH 5.2, 7, and 9.3, respectively, which are approximately 1-2 orders of magnitude higher than for weak S2 sites. The results suggest that AsIII complexation with DOM increases with pH, as evidenced by significant spikes in concentrations of DOM-bound AsIII and in KD values at pH 9.3. In contrary to KD, logKs decreased with pH, in particular for S1 sites, probably due to the presence of negatively charged H2AsO3- and the involvement of metal-bridged AsIII-DOM complexation at pH 9.3.

Degradation of methylmercury and its effects on mercury distribution and cycling in the Florida Everglades.

Methylmercury (MeHg) is recognized as one of the major water quality concerns in the Florida Everglades. Degradation of MeHg in the water is thought to be one of the most important processes to the cycling of MeHg, but there is a lack of quantitative estimations of its effect on the distribution and cycling of MeHg in this ecosystem. Stable isotope (Me201Hg) addition method was implemented to investigate the degradation of MeHg in the Everglades. By combining these results with the field monitoring data, effects of photodegradation on MeHg distribution and its contribution to MeHg cycling were estimated. The results indicate that degradation of MeHg in Everglades water is mediated by sunlight and that UV-A and UV-B radiations are the principal driver. The spatial pattern of MeHg photodegradation potential (PPD) generally illustrated an increasing trend from north to south in the Everglades, which was opposite to the distribution of MeHg in water column. Correlation analysis shows that MeHg concentration in the water had a significant negative relation to PPD, suggesting that photodegradation could play an important role in controlling the distribution of MeHg in Everglades water. Furthermore, about 31.4% of MeHg input into the water body was removed by photodegradation, indicating its importance in the biogeochemical cycling of MeHg in the Everglades. This percent reduction is much lower than that reported for other ecosystems, which could be caused by the higher concentration of DOC in the Everglades. The relatively slower degradation of MeHg could be one of the main reasons for the high ratio of MeHg to total mercury (THg) in this ecosystem.

Simultaneous Speciation of Monomethylmercury and Monoethylmercury by Aqueous Phenylation and Purge-and-Trap Preconcentration Followed by Atomic Spectrometry Detection

A new method for the detection of trace levels of organomercury species has been developed by combining the high enrichment capacity of purge and trap with aqueous phenylation derivatization. Phenylation products of monomethylmercury (MeHg) and monoethylmercury (EtHg) were first separated by capillary gas chromatography and then detected by atomic fluorescence spectrometry (AFS) or inductively coupled plasma mass spectrometry (ICPMS). This combination made it possible to simultaneously quantify trace or ultratrace level of MeHg and EtHg in environmental samples. Method detection limits were 0.03 ng/L for both MeHg and EtHg when AFS was used as the detector and 0.02 and 0.01 ng/L for MeHg and EtHg with ICPMS, respectively. Certified reference materials, IAEA-405 and DORM-2, were analyzed and the results were in accordance with certified values. Both MeHg and EtHg were detected in sediment samples collected from the Florida Everglades and a Canadian wetland. This new method has been validated for the direct detection of trace organomercury species in freshwater samples and has the additional benefits of being free from interference by Cl (-) and dissolved organic matter.

Role of soil-derived dissolved substances in arsenic transport and transformation in laboratory experiments

Dissolved substances derived from soil may interact with both soil surfaces and with arsenic and subsequently influence arsenic mobility and species transformation. The purpose of this study was to investigate arsenic transport and transformation in porous media with a specific focus on the impact of soil-derived dissolved substances, mainly consisting of inorganic colloids and dissolved organic matter (DOM), on these processes. Arsenic transport and transformation through columns, which were packed with uncoated sand (UC) or naturally coated sand (NC) and fed with arsenate (AsV) or monomethylarsonic acid (MMA) spiked influents, were investigated in the presence or absence of soil-derived dissolved substances. The presence of soil-derived inorganic colloids and/or DOM clearly enhanced As transport through the column, with the fraction of As leached out of column (referring to the total amount added) being increased from 23 to 46% (UC) and 21 to 50% (NC) in AsV experiments while 46 to 64% (UC) and 28 to 63% (NC) in MMA experiments. The association of arsenic with DOM and the competitive adsorption between arsenic and DOM could account for, at least partly, the enhanced As movement. Distinct species transformation of As during transport through soil columns was observed. When AsV was the initial species spiked in the influent solutions, only arsenite (AsIII) was detected in the effluents for UC columns; while both AsIII (dominant) and AsV were present for NC columns, with AsIII being the dominant species. When MMA was initially spiked in the influent solutions, all method detectable As species, AsIII, AsV, MMA, and dimethylarsenic acid (DMA) were present in the effluents for both soil columns. These results indicate that risk assessment associated with As contamination, particularly due to previous organoarsenical pesticide applications, should take into account the role of soil-derived dissolved substances in promoting As transport and As species transformation.

Estimation of the Major Source and Sink of Methylmercury in the Florida Everglades

Mercury methylation and/or demethylation have been observed in several compartments [soil (saturated soils covered by standing water), floc, periphyton, and water] of the Everglades, a wetland with mercury as one of the major water quality concerns. However, it is still unclear which compartment is the major source or sink due to the lack of estimation and comparison of the net methylmercury (MeHg) production or degradation in these compartments. The lack of this information has limited our understanding of Hg cycling in this ecosystem. This study adopted a double stable isotope ((199)Hg(2+) and Me(201)Hg) addition technique to determine the methylation/demethylation rate constants and the net MeHg production rates in each compartment. This study improved the previous models for estimating these parameters by (1) taking into account the difference between newly input and ambient mercury in methylation/demethylation efficiency and (2) correcting the contribution of photodemethylation to Me(199)Hg concentration when calculating methylation rates in water. The net MeHg production rate in each compartment was then estimated to identify the major sources and sinks of MeHg. The results indicate that these improvements in modeling are necessary, as a significant error would occur otherwise. Soil was identified to be the largest source of MeHg in the Everglades, while the floc and water column were identified as the major sinks. The role of periphyton varies, appearing to be a source in the northern Everglades and a sink in the southern Everglades. Soil could be the largest source for MeHg in the water column, while methylation in periphyton could also contribute significantly in the northern Everglades.

Evaluation of the Possible Sources and Controlling Factors of Toxic Metals/Metalloids in the Florida Everglades and Their Potential Risk of Exposure.

The Florida Everglades is an environmentally sensitive wetland ecosystem with a number of threatened and endangered fauna species susceptible to the deterioration of water quality. Several potential toxic metal sources exist in the Everglades, including farming, atmospheric deposition, and human activities in urban areas, causing concerns of potential metal exposure risks. However, little is known about the pollution status of toxic metals/metalloids of potential concern, except for Hg. In this study, eight toxic metals/metalloids (Cd, Cr, Pb, Ni, Cu, Zn, As, and Hg) in Everglades soils were investigated in both dry and wet seasons. Pb, Cr, As, Cu, Cd, and Ni were identified to be above Florida SQGs (sediment quality guidelines) at a number of sampling sites, particularly Pb, which had a level of potential risk to organisms similar to that of Hg. In addition, a method was developed for quantitative source identification and controlling factor elucidation of toxic metals/metalloids by introducing an index, enrichment factor (EF), in the conventional multiple regression analysis. EFs represent the effects of anthropogenic sources on metals/metalloids in soils. Multiple regression analysis showed that Cr and Ni were mainly controlled by anthropogenic loading, whereas soil characteristics, in particular natural organic matter (NOM), played a more important role for Hg, As, Cd, and Zn. NOM may control the distribution of these toxic metals/metalloids by affecting their mobility in soils. For Cu and Pb, the effects of EFs and environmental factors are comparable, suggesting combined effects of loading and soil characteristics. This study is the first comprehensive research with a vast amount of sampling sites on the distribution and potential risks of toxic metals/metalloids in the Everglades. The finding suggests that in addition to Hg other metals/metalloids could also potentially be an environmental problem in this wetland ecosystem.

Legacy and Fate of Mercury and Methylmercury in the Florida Everglades

Mass inventories of total Hg (THg) and methylmercury (MeHg) and mass budgets of Hg newly deposited during the 2005 dry and wet seasons were constructed for the Everglades. As a sink for Hg, the Everglades has accumulated 914, 1138, 4931, and 7602 kg of legacy THg in its 4 management units, namely Water Conservation Area (WCA) 1, 2, 3, and the Everglades National Park (ENP), respectively, with most Hg being stored in soil. The current annual Hg inputs account only for 1-2% of the legacy Hg. Mercury transport across management units during a season amounts to 1% or less of Hg storage, except for WCA 2 where inflow inputs can contribute 4% of total MeHg storage. Mass budget suggests distinct spatiality for cycling of seasonally deposited Hg, with significantly lower THg fluxes entering water and floc in ENP than in the WCAs. Floc in WCAs can retain a considerable fraction (around 16%) of MeHg produced from the newly deposited Hg during the wet season. This work is important for evaluating the magnitude of legacy Hg contamination and for predicting the fate of new Hg in the Everglades, and provides a methodological example for large-scale studies on Hg cycling in wetlands.

Occurrence of monoethylmercury in the Florida Everglades: Identification and verification

A few studies have reported the occurrence of monoethylmercury (CH(3)CH(2)Hg(+)) in the natural environment, but further verification is needed due to the lack of direct evidence and/or uncertainty in analytical procedures. Various analytical techniques were employed to verify the occurrence of CH(3)CH(2)Hg(+) in soil of the Florida Everglades. The identity of CH(3)CH(2)Hg(+) in Everglades soil was clarified, for the first time, by GC/MS. The employment of the recently developed aqueous phenylation-purge-and-trap-GC coupled with ICPMS confirmed that the detected CH(3)CH(2)Hg(+) was not a misidentification of CH(3)SHg(+). Stable isotope-tracer experiments further indicated that the detected CH(3)CH(2)Hg(+) indeed originated from Everglades soil and was not an analytical artifact. All these evidence clearly confirmed the occurrence of CH(3)CH(2)Hg(+) in Everglades soil, presumably as a consequence of ethylation occurring in this wetland. The prevalence of CH(3)CH(2)Hg(+) in Everglades soil suggests that ethylation could play an important role in the biogeochemical cycling of Hg.

Studying arsenite–humic acid complexation using size exclusion chromatography–inductively coupled plasma mass spectrometry

Arsenic (As) can form complexes with dissolved organic matter (DOM), which affects the fate of arsenic in waste sites and natural environments. It remains a challenge to analyze DOM-bound As, in particular by using a direct chromatographic separation method. Size exclusion chromatography (SEC) hyphenated with UV spectrophotometer and inductively coupled plasma mass spectrometry (ICP-MS) was developed to characterize the complexation of arsenite (As(III)) with DOM. This SEC-UV-ICP-MS method is able to differentiate As(III)-DOM complexes from free As species and has the advantage of direct determination of both free and DOM-bound As(III) through mild separation. The suitability of this method for studying As(III)-DOM complexation was demonstrated by its application, in combination with the Scatchard plot and nonlinear regression of ligand binding model, for characterizing As(III) complexation with humic acid (HA) in the absence or presence of natural sand. The results suggest that, consistent with polyelectrolytic nature of HA, the As(III)-HA complexation should be accounted for by multiple classes of binding sites. By loosely classifying the binding sites into strong (S1) and weak (S2) sites, the apparent stability constants (Ks) of the resulting As-DOM complexes were calculated as logK(s1) = 6.5-7.1 while logK(s2) = 4.7-5.0.

Elemental Mercury in Natural Waters: Occurrence and Determination of Particulate Hg(0)

Elemental mercury, Hg(0), is ubiquitous in water and involved in key Hg biogeochemical processes. It is extensively studied as a purgeable dissolved species, termed dissolved gaseous mercury (DGM). Little information is available regarding nonpurgeable particulate Hg(0) in water, Hg(0) bound to suspended particulate matter (SPM), which is presumably present due to high affinity of Hg(0) adsorption on solids. By employing stable isotope tracer and isotope dilution (ID) techniques, we investigated the occurrence and quantification of particulate Hg(0) after Hg(0) being spiked into natural waters, aiming to provide firsthand information on particulate Hg(0) in water. A considerable fraction of (201)Hg(0) spiked in water (about 70% after 4 h equilibration) was bound to SPM and nonpurgeable, suggesting the occurrence of particulate Hg(0) in natural waters. A scheme, involving isotope dilution, purge and trap, and inductively coupled plasma mass spectrometry detection, was proposed to quantify particulate Hg(0) by the difference between DGM and total Hg(0), determined immediately and at equilibration after spiking ID Hg isotope, respectively. The application of this newly established method revealed the presence of particulate Hg(0) in Florida Everglades water, as the determined DGM levels (0.14 to 0.22 ng L(-1)) were remarkably lower than total Hg(0) (0.41 to 0.75 ng L(-1)).